CN107522801B - Propylene-butene copolymerization catalyst system and application thereof in preparation of propylene-butene copolymer - Google Patents
Propylene-butene copolymerization catalyst system and application thereof in preparation of propylene-butene copolymer Download PDFInfo
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- CN107522801B CN107522801B CN201610459457.8A CN201610459457A CN107522801B CN 107522801 B CN107522801 B CN 107522801B CN 201610459457 A CN201610459457 A CN 201610459457A CN 107522801 B CN107522801 B CN 107522801B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
Abstract
The invention discloses a propylene-butene copolymerization catalyst system and application thereof in preparation of propylene-butene copolymer, wherein a main catalyst in the catalyst system is MgCl2/ID/TiCl4The supported catalyst and the cocatalyst are mixed AlX3The external electron donor is R1R2Si(OCH3)2、R3R4Si(OCH3)2The mixture of the two; wherein the ID is an organic electron donor, and the specific surface area of the main catalyst is 250-500 m2(iii) the particle size distribution range is 5-150 microns. The crystalline fraction of the propylene butene copolymer prepared by the process of the present invention has a longer propylene sequence. The modified polybutene material with excellent rigidity and toughness balance performance is obtained by toughening and modifying isotactic polypropylene with the propylene-butylene copolymer with the special structure.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a propylene-butylene copolymerization catalyst system and application thereof in preparation of a propylene-butylene copolymer.
Background
The propylene-butylene copolymer is a synthetic polymer material with wide application, can be used as a biaxially oriented polypropylene film, has the characteristics of high strength, light weight, good gas barrier property, good printing property, strong tear resistance and the like, is a variety with the largest consumption in polypropylene film products, and is widely applied to various packaging products. The homo-polypropylene has a regular molecular structure and high rigidity, and the performance of the homo-polypropylene in preparing a film is poorer than that of the random polypropylene. The random copolymerization polypropylene has proper isotacticity, and a small amount of 1-butene is added in the polymerization process for copolymerization, so that the molecular structure, the molecular weight distribution and the tensile property of the polypropylene are improved, and the film product has high crystallization rate and good transparency. Compared with propylene ethylene random copolymer, the propylene butylene random copolymer has the outstanding characteristics of good balance of transparency, rigidity and surface non-adhesiveness, low room-temperature soluble substance content and less surface precipitates of corresponding films or products. At present, two types of catalyst systems are mainly adopted, wherein one type is a metallocene catalyst system; another class is Ziegler-Natta catalyst systems. Previous studies have shown that, in the propylene-butene random copolymer prepared by the titanium-based catalyst system, 80% of butene is inserted into the propylene-butene copolymer chain in a monomolecular manner and 20% of butene is inserted into the propylene-butene copolymer chain in two to three structural units due to the relatively small amount of butene added. The crystalline fraction consists of a series of compositionally different propylene-butene multiblock copolymers in which the butene units are present in essentially monomolecular form.
In the catalyst system for preparing propylene-butene copolymer, the main catalyst (supported titanium catalyst) composed of magnesium chloride supported by titanium chloride, and the alkyl aluminum cocatalyst (AlX)3X is alkyl with 1-8 carbon atoms) and a small amount of organic electron donor compound (called as external electron donor) is added, wherein the general formula is R1R2Si(OCH3). The organosilicon oxygen compound is the most commonly used external electron donor, where R is1And R2Alkyl containing 1-20 carbon atoms, cycloalkyl or phenyl with substituent groups, and organosilicon external electron donors with different structures are added into a supported titanium catalyst system to adjust the isotacticity of the polypropylene in Chinese patent 98126383.6. The report of using a mixed cocatalyst and a mixed external electron donor to adjust the propylene and butylene copolymerization characteristics of the supported titanium catalyst is not seen in the published literature.
Disclosure of Invention
The object of the present invention is to provide a propylene butene copolymerization catalyst system with which propylene butene copolymers can be obtained by polymerization reactions to obtain propylene butene block copolymer fractions containing longer propylene sequences.
In order to achieve the purpose, the invention adopts the following technical scheme: a catalyst system for copolymerizing propylene and butylene features that the MgCl is used as main catalyst2/ID/TiCl4The supported catalyst and the cocatalyst are mixed AlX3The external electron donor is R1R2Si(OCH3)2、R3R4Si(OCH3)2The mixture of the two; wherein the ID is an organic electron donor, and the specific surface area of the main catalyst is 250-500 m2(iii) the particle size distribution range is 5-150 microns.
The main catalyst comprises the following components in percentage by weight: 1.5 to 3.5 percent of titanium, 52 to 65 percent of chlorine, 10 to 23 percent of magnesium, 6.0 to 20.0 percent of ID and 1 to 6 percent of inert solvent.
The ID is one of or a mixture of any two of diisobutyl phthalate, di-n-butyl phthalate, 9-bis (methylmethoxy) fluorene, 9-bis (phenylcarboxymethyl) fluorene, 2-isopropyl-2-isoamyl-1, 3-diphenylcarboxy propane and 2, 2-diisobutyl-1, 3-diphenylcarboxy propane.
The cocatalyst is a mixture of triethyl aluminum, triisobutyl aluminum and trimethyl aluminum, the molar ratio of aluminum in the cocatalyst to titanium in the main catalyst is 40-400: 1, and the molar ratio of aluminum in the cocatalyst to silicon in the external electron donor is 3-30: 1.
The R is1R2Si(OCH3)2、R3R4Si(OCH3)2In R1、R2、R3、R4Respectively, alkyl groups with 1-12 carbon atoms, cycloalkyl groups or phenyl groups with substituents which are the same or different.
A polymerization reaction process of a slurry method or a gas phase method is adopted, the copolymerization of propylene and butylene is carried out in an intermittent or continuous reaction mode, a solvent is straight-chain alkane or cycloalkane of C5-C10, a molecular weight regulator is hydrogen, the pressure in a reaction kettle is 0.1-3.0 MPa, and the retention time of reactants is 0.2-2 hours.
The specific process of the intermittent slurry polymerization process for propylene and butylene copolymerization comprises the following steps: adding a purified dry hydrocarbon solvent into a kettle type reactor, adding a mixed cocatalyst and a mixed external electron donor into the reactor after the reactor is heated to a preset temperature, pressing propylene/butylene mixed gas with set pressure into the reactor under stirring until gas-liquid balance is achieved, adding main catalyst powder or slurry thereof into the reactor to start polymerization, removing monomer pressure after the reaction is finished, and removing residual monomer and solvent under reduced pressure to obtain copolymer particles.
The preparation method of the propylene butene copolymer can adopt two specific embodiments that firstly, propylene and butene are subjected to slurry copolymerization in a hydrocarbon solvent containing a catalyst system and a small amount of hydrogen to obtain a viscous solution of the copolymer after reacting for a certain time, the hydrocarbon solvent in the solution is removed to obtain a solid propylene butene copolymer, secondly, gaseous propylene and butene are subjected to gas phase copolymerization in the presence of the catalyst system and a small amount of hydrogen to directly synthesize granular propylene butene copolymer, the used catalyst system consists of three components of a titanium system supported main catalyst, a cocatalyst and an organic silicon external electron donor, and the preparation method of the main catalyst can be referred to published patent documents (such as Z L85100997, Z L93102795.0, Z L01258684, Z L1298887, Z L1298888, Z L1436766, Z L1436796, Z L1436760, Z L02100897.3, Z L021000894.9 and Z L03109781.2).
According to the interaction among the components of the catalytic system, the alkylaluminum not only alkylates and reduces titanium on the surface of the catalyst to a lower valence state, but also forms a complex with the methoxysilane due to the strong L ewis acidity, the external electron donor basically complexes and coordinates the coordinated unsaturated Mg beside the active center through an electron supply group (methoxy) of the alkylaluminum, and the stereogenic effect of the alkylaluminum improves the orientation capability of the active center, however, the alkylaluminum located outside the surface of the catalyst has the strong L ewis acidity, and can also form a coordination complex with the external electron donor.
The main advantages of the invention are: the copolymer with longer propylene sequence and crystalline fraction can be obtained by copolymerization of propylene and butylene by adopting a conventional high-efficiency supported catalyst for preparing isotactic polypropylene and simultaneously using a mixed cocatalyst and a mixed external electron donor. The propylene-butylene copolymer with the special structure is used for toughening and modifying the isotactic polypropylene to obtain the propylene-butylene copolymer material with better impact resistance effect and excellent rigidity-toughness balance performance. Because the spherical high-efficiency supported Ziegler-Natta catalyst taking magnesium chloride as a carrier is adopted, the propylene-butene copolymer obtained by polymerization in the steps is obtained by adding a mixed cocatalyst and a mixed external electron donor into a propylene-butene copolymerization system, and compared with a polymerization system only adding a single cocatalyst and a single external electron donor, the average length of a propylene sequence of a crystalline fraction in the propylene-butene copolymer is increased by more than 20%.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
The catalytic efficiency of the reaction is expressed in grams of copolymer produced per gram of catalyst per hour (g polymer/g catalyst. multidot. hr). The crystalline fraction content of the propylene butene copolymer was determined by the dissolution separation method, namely: the copolymer was first dissolved in boiling n-octane, the solution was then cooled to room temperature to precipitate a solid crystalline fraction, which was isolated by filtration, dried and weighed. The molecular weight and molecular weight distribution of the propylene butene copolymer were determined by gel permeation chromatography analysis. Butene unit content and average length of propylene sequences (n) of the crystalline fraction in the copolymerp) Measured by nuclear magnetic resonance carbon spectrometry.
Example 1
The reactor for preparing the propylene-butene copolymer is a steel pressure-resistant reaction kettle with a mechanical stirring device and a temperature control jacket, the volume of the kettle is 1L, the bottom and the cover of the reaction kettle are respectively provided with a gaseous monomer feed inlet and a valve, the cover of the reaction kettle is also provided with a catalyst feed inlet, a pressure gauge and an exhaust pipeline with a pressure controller, before the reaction, the kettle is heated to 100 ℃, the kettle is vacuumized for 2 hours through the catalyst feed inlet to remove water and air in the kettle, then the temperature of the kettle is controlled to 70 ℃, the stirring speed is adjusted to 300 r/m, propylene/butene mixed gas with the molar ratio of 2:1 is added into the kettle to 0.1MPa (absolute pressure, the following pressures are absolute pressures), 20m L hydrogen is added, hexane 500m L is added through the feed inlet of the cover of the kettle, and metered co-catalysts are sequentially added from the catalyst feed inlet, and Al (C) with the molar ratio of 4:12H5)3/Al(i-C4H9)3Mixture, 2M hexane solution, metered external electron donor, methylcyclopentyldimethoxysilane/dicyclopentyldimethoxysilane mixture in a molar ratio of 4:1, 0.5M hexane solution, 49.8mg MgCl2/ID/TiCl4A supported catalyst. The molar ratio of aluminum in the cocatalyst to titanium in the main catalyst is 100:1, and the molar ratio of aluminum in the cocatalyst to silicon in the external electron donor is 20. By continuously supplying a propylene/butene mixed gas with a partial pressure ratio of 1:2 to 0.4MPa, the kettle temperature is 70 ℃, and the reaction time is 30 min. And discharging the gas in the kettle after 30min, pouring the gas into a beaker, and removing the solvent to obtain the propylene-butylene copolymer. The catalytic efficiency of the copolymerization was 1278g polymer/g cat h. The weight average molecular weight of the propylene-butene copolymer was 19 ten thousand, and the molecular weight distribution was 4.5. The crystalline fraction content of the copolymer was 19%. The butene content of the crystalline fraction was 12% (mol) and the average length of the propylene sequences was 2.8.
Example 2
In example 2, 48.9mg of the main catalyst was used, and Al (C) was used as a mixed cocatalyst2H5)3/Al(i-C4H9)3The molar ratio was 1:1(2M hexane solution), and the remaining operating and polymerization conditions were the same as in example 1. The catalytic efficiency of the copolymerization was 1368g polymer/g cat h. The weight average molecular weight of the propylene-butene copolymer was 18 ten thousand, and the molecular weight distribution was 4.8. The crystalline fraction content of the copolymer was 21%. The butene content of the crystalline fraction was 13% (mol) and the average length of the propylene sequences was 3.1.
Example 3
In example 3, the main catalyst was used in an amount of 49.2mg, and the mixed external electron donor methylcyclopentyldimethoxysilane/dicyclopentyldimethoxysilane molar ratio was 1:1(0.5M hexane solution), and the other operation and polymerization conditions were the same as in example 1. The catalytic efficiency of the copolymerization was 1301g of polymer/g of catalyst/hr. The weight average molecular weight of the propylene-butene copolymer was 21 ten thousand, and the molecular weight distribution was 4.4. The crystalline fraction content of the copolymer was 22%. The butene content of the crystalline fraction was 16% (mol) and the average length of the propylene sequences was 2.9.
Example 4
In example 4, 49.0mg of the main catalyst was used, and Al (C) as a mixed co-catalyst was used2H5)3/Al(i-C4H9)3The molar ratio of methyl cyclopentyldimethoxysilane/dicyclopentyldimethoxysilane was 1:1(2M in hexane) and the external electron donor was mixed in a molar ratio of 1:1(0.5M in hexane), and the rest of the procedure and polymerization conditions were the same as in example 1. The catalytic efficiency of the copolymerization was 1421g of polyCompound/g catalyst/hr. The weight average molecular weight of the propylene-butene copolymer was 23 ten thousand, and the molecular weight distribution was 4.5. The crystalline fraction content of the copolymer was 22%. The butene content of the crystalline fraction was 15% (mol) and the average length of the propylene sequences was 3.1.
Comparative example 5
In comparative example 5, the amount of the main catalyst was 49.5mg, and the cocatalyst used was Al (C)2H5)3(2M in hexane), the external electron donor is methylcyclopentyldimethoxysilane (0.5M in hexane), and the remaining operating and polymerization conditions were the same as in example 1. The catalytic efficiency of the copolymerization was 1314g polymer/g cat h. The weight average molecular weight of the propylene-butene copolymer was 17 ten thousand, and the molecular weight distribution was 5.0. The crystalline fraction content of the copolymer was 18%. The butene content of the crystalline fraction was 14% (mol) and the average length of the propylene sequences was 2.6.
Although the embodiments of the present invention have been described in detail with reference to the examples, it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the claims. Those skilled in the art can appropriately modify the embodiments without departing from the technical spirit and scope of the present invention, and the modified embodiments are also clearly included in the scope of the present invention.
Claims (5)
1. A propylene butene copolymerization catalyst system, characterized by: the main catalyst is MgCl2/ID/TiCl4The supported catalyst and the cocatalyst are mixed AlX3The external electron donor is R1R2Si(OCH3)2、R3R4Si(OCH3)2The mixture of the two; wherein the ID is an organic electron donor, and the specific surface area of the main catalyst is 250-500 m2(ii)/g, the particle size distribution range is 5-150 microns;
the R is1R2Si(OCH3)2、R3R4Si(OCH3)2In R1、R2、R3、R4Respectively, alkyl, cycloalkyl or phenyl with substituent groups with the same or different carbon numbers of 1-12;
the cocatalyst is a mixture of triethyl aluminum, triisobutyl aluminum and trimethyl aluminum, the molar ratio of aluminum in the cocatalyst to titanium in the main catalyst is 40-400: 1, and the molar ratio of aluminum in the cocatalyst to silicon in the external electron donor is 3-30: 1.
2. The propylene butene copolymerization catalyst system according to claim 1, characterized in that: the main catalyst comprises the following components in percentage by weight: 1.5 to 3.5 percent of titanium, 52 to 65 percent of chlorine, 10 to 23 percent of magnesium, 6.0 to 20.0 percent of ID and 1 to 6 percent of inert solvent.
3. The propylene butene copolymerization catalyst system according to claim 2, characterized in that: the ID is one of or a mixture of any two of diisobutyl phthalate, di-n-butyl phthalate, 9-bis (methylmethoxy) fluorene, 9-bis (phenylcarboxymethyl) fluorene, 2-isopropyl-2-isoamyl-1, 3-diphenylcarboxy propane and 2, 2-diisobutyl-1, 3-diphenylcarboxy propane.
4. Use of the catalyst according to any one of claims 1 to 3 for the preparation of propylene butene copolymers, characterized in that: the polymerization process of the slurry method or the gas phase method is adopted, the copolymerization of propylene and butylene is carried out in an intermittent or continuous reaction mode, the solvent is straight-chain alkane or cycloalkane of C5-C10, the molecular weight regulator is hydrogen, the pressure in the reaction kettle is 0.1-3.0 MPa, and the retention time of reactants is 0.2-2 hours.
5. Use according to claim 4, characterized in that: the specific process of the intermittent slurry polymerization process for propylene and butylene copolymerization comprises the following steps: adding a purified dry hydrocarbon solvent into a kettle type reactor, adding a mixed cocatalyst and a mixed external electron donor into the reactor after the reactor is heated to a preset temperature, pressing propylene/butylene mixed gas with set pressure into the reactor under stirring until gas-liquid balance is achieved, adding main catalyst powder or slurry thereof into the reactor to start polymerization, removing monomer pressure after the reaction is finished, and removing residual monomer and solvent under reduced pressure to obtain copolymer particles.
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| US4968653A (en) * | 1989-06-30 | 1990-11-06 | Quantum Chemical Corporation | Propylene polymerization catalyst |
| US6534613B2 (en) * | 1998-02-18 | 2003-03-18 | Eastman Chemical Company | Process for producing polyethylene |
| CN101993510A (en) * | 2009-08-14 | 2011-03-30 | 中国石油化工股份有限公司 | Method for preparing ethylene-propylene copolymer |
| CN103130939A (en) * | 2013-03-18 | 2013-06-05 | 中国石油化工股份有限公司 | Production method of propylene/1-butene random copolymer |
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| FI76354C (en) * | 1986-12-31 | 1988-10-10 | Neste Oy | CATALYTIC COMPONENT FOER ZIEGLER-NATTA CATALYST OCH FOERFARANDE FOER POLYMERIZERING AV -OLEFINER. |
| KR910005678B1 (en) * | 1987-07-20 | 1991-08-01 | 이데미쯔세끼유 가가꾸 가부시기가이샤 | Butene - 1 copolymer |
| US5637665A (en) * | 1992-09-08 | 1997-06-10 | Rexene Corporation | High tensile strength amorphous 1-butene/propylene and ethlene/propylene copolymers |
| DE19533337A1 (en) * | 1995-09-11 | 1997-03-13 | Basf Ag | Propene / but-1-ene copolymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4968653A (en) * | 1989-06-30 | 1990-11-06 | Quantum Chemical Corporation | Propylene polymerization catalyst |
| US6534613B2 (en) * | 1998-02-18 | 2003-03-18 | Eastman Chemical Company | Process for producing polyethylene |
| CN101993510A (en) * | 2009-08-14 | 2011-03-30 | 中国石油化工股份有限公司 | Method for preparing ethylene-propylene copolymer |
| CN103130939A (en) * | 2013-03-18 | 2013-06-05 | 中国石油化工股份有限公司 | Production method of propylene/1-butene random copolymer |
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